CN104321415A - Method for preparing biodiesel - Google Patents

Method for preparing biodiesel Download PDF

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Publication number
CN104321415A
CN104321415A CN201480000797.3A CN201480000797A CN104321415A CN 104321415 A CN104321415 A CN 104321415A CN 201480000797 A CN201480000797 A CN 201480000797A CN 104321415 A CN104321415 A CN 104321415A
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China
Prior art keywords
oil
raw material
biodiesel raw
reaction
catalyst
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CN201480000797.3A
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Chinese (zh)
Inventor
河泰豪
全裕珍
高正焕
尹俊又
李承敦
朴赫
郭珍植
李康勳
金景洙
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Kk Mreserchinstitute
Mreserchinstitute
Kk Menergy
Menergy
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Kk Mreserchinstitute
Kk Menergy
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Publication of CN104321415A publication Critical patent/CN104321415A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/08—Drying or removing water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/26—Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Fats And Perfumes (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

Disclosed herein is a method of preparing biodiesel, including the steps of: removing foreign materials from biodiesel raw oil containing lower fatty acid and having an acid value of 20 mgKOH/g or less with an adsorbent; dewatering the foreign materials removed biodiesel raw oil; passing the dewatered biodiesel raw oil through a solid acid catalyst reaction guard bed provided with a cation exchange resin for removing metal cations at 20-80 DEG C at a flow rate of 6 vol% (6 SV) or less, mixing methanol with the passed biodiesel raw oil, and then passing the mixture through a solid acid catalyst reaction main bed provided with a solid acid catalyst for an esterification reaction at 70-120 DEG C at a flow rate of 0.5-1.5 SV to adjust a final acid value of the biodiesel raw oil to 5 mgKOH/g or less; and reacting the biodiesel raw oil having the final acid value of 5 mgKOH/g or less in the presence of an alkali catalyst.

Description

Prepare the method for biofuel
Technical field
The present invention relates to the method preparing biofuel.
Background technology
Along with industrial expansion, the application comprising the industrial machine of diesel motor increases, and automobile has become essential for the modern life, the production of automobile has simultaneously increased in the whole world, and the consumption being therefore used as the diesel oil of the raw material of diesel-engined vehicle too increases.Diesel oil is one of fuel obtained from crude oil, and its advantage is that it has high burning efficiency, cheap, and decreases carbonic acid gas (CO 2) generation.But the problem of diesel oil is to compare other fuel obtained from crude oil, and diesel oil discharges a large amount of air pollutant after being combusted.
In order to solve the above problems, carried out much research find there is physical properties similar to diesel oil, economical and air-polluting alternative fuel can be prevented on producing.This research as a result, many focuses have invested biofuel, it is the natural circulatory energy and has the physical properties similar to diesel oil, significantly can reduce the discharge of air pollutant and can show and reduce carbonic acid gas (CO 2) effect.
Therefore, due to the exhaustion of petroleum-based energy, many countries have actively added production and the use of the biofuel of renewable energy source as an alternative, and reduce the carbonic acid gas generation caused due to excessive use fossil oil.
Biofuel refers to the ester oil prepared by various renewable source and alcohol reaction in the presence of a catalyst, and renewable source is as each vegetable oil (comprising rapeseed oil, soybean oil, palm wet goods), animal oil (comprising tallow etc.) and cooking waste oil.Because biofuel and diesel oil have similar physical properties, it can replace diesel oil or combine for compression ignition-type diesel oil internal combustion engine with diesel oil.That is, biofuel can be defined as the alternative fuel of diesel oil, and it is prepared by the chemical reaction of animal or plant lipid acid and methyl alcohol.
So, prepare biofuel by the reaction of fatty alcohol (as methyl alcohol) and animal or plant oil, and in this case, the seed output and quality of biofuel depends on the animal or plant oil properties of the raw material as biofuel.Unpurified animal or plant oil is used to there is many problems, such as output reduction, quality deterioration etc. in building-up process as the biofuel of raw material production.
In order to solve the problem of seed output and quality, most biofuel manufacturers has used the edible soybean oil of purifying or vegetable seed wet goods as the raw material of biofuel.But, use food source to cause many problem incoherent with the original pursuit of substitute energy as the energy, and improper in economical efficiency, because edible soybean oil or rapeseed oil are expensive.
In the whole world, be converted into now the raw material that byproduct or the oil of the animal and plant after using or fat are widely used as charging or soap most in a large number.The fat of some animal and plants and oil (impurity comprises the free fatty acids (FFA) of 2.0% or lower) is simply separated and after chemical refining process as the raw material of biofuel.
Simultaneously, containing have 5mgKOH/g or more high acid value lower fatty acid (such as, rudimentary cooking waste oil, by the palmitic acid oil that plam oil basic refining obtains, the brown grease obtained from food waste, the dark oil (soap stock) obtained from alkaline putty, the white grease obtained by the preliminary refining of dark oil and yellow grease, from irrigation canals and ditches, the oil removal etc. obtained in water shoot) biodiesel raw material oil, and the oil & fat of the animal and plant containing a large amount of non-purifying impurity comprises a large amount of particulate matters, glue, lipid acid, soap and moisture etc., and the deterioration of the seed output and quality of biofuel can be caused in the process being prepared biofuel by methyl esterification of fatty acid.
In other words, the particulate matter comprised at the oil & fat of cooking waste oil or the animal and plant containing a large amount of non-purifying impurity causes following problem: the blocking of biofuel Preparation equipment, reduces the output of biofuel, pollutes distil process and deteriorates the quality of by-product glycerin.
Particularly, in the synthesis of biofuel, FFA (free fatty acids) and basic catalyst react and form soap and the loss causing basic catalyst.In this case, due to the soap formed, biofuel and glycerine emulsified, and be therefore difficult to by biofuel and glycerine separated from each other, thus reduce the output of biofuel and the quality of deteriorated biofuel.In addition, due to the water formed in the reaction, biofuel is hydrolyzed by water and forms FFA (free fatty acids), DAG (DG ester) and MAG (monoacylglycerol ester).
Namely, the soap contained in biodiesel raw material oil or the soap component formed in the building-up process of biofuel and oily part emulsification, so be difficult to they are separated from each other, result is that the output of biofuel reduces, the quality deterioration of biofuel, quality as the glycerine of by product is also deteriorated, and the aftertreatment technology of by product becomes complicated.
Meanwhile, patent documentation 1 discloses the method that the oil & fat containing the animal and plant of a large amount of impurity by refining prepares biodiesel raw material oil; Patent documentation 2 discloses the method using heterogeneous solid acid catalyst to remove the free fatty acids contained in cooking waste oil; And patent documentation 3 discloses the method preparing biofuel, wherein remove the water that comprises of alcohol by pervaporation, this alcohol reclaims by the process preparing biofuel from the oil & fat containing free fatty acids, and this alcohol resupplies reactor makes water reduce for the effect of esterification and transesterification reaction, thus adds purity and the output of biofuel.
In the methods described above, known basic catalyst, alkoxide catalysis, solid acid catalyst or metal catalyst etc. are used usually to prepare biofuel by continuous or interrupter method.But at present, the problem of these class methods is efficiently to process all kinds and low-quality biodiesel raw material oil.
Patent documentation 1: Korean patent registration No. 10-0950280
Patent documentation 2: Korean Patent Publication No 2004-0087625
Patent documentation 3: Korean Patent Publication No 2009-0129619
Summary of the invention
Technical problem
Therefore, the present inventor finds when according to its physical properties, optionally pre-treat biological diesel raw material is oily, so that the acid number of biodiesel raw material oil is controlled to preset value or lower, then combine and implement biocatalysis agent method, solid acid catalyst processes and base metal catalysts method, the reactivity of catalyzer is efficiently increased, high-grade biofuel can be prepared economically, as automobile fuel.The present invention is completed based on these discoveries.
Therefore, the object of this invention is to provide a kind of method, the method uses the combination of biocatalysis agent method, solid acid catalyst processes and base metal catalysts method, economical and prepare biofuel efficiently.
Another object of the present invention is to provide a kind of method, and the method uses the combination of enzyme catalyst method, solid acid catalyst processes and base metal catalysts method, economical and prepare biofuel efficiently.
Technical scheme
In order to achieve the above object, first aspect of the present invention provides the method preparing biofuel, said method comprising the steps of: contain lower fatty acid by sorbent treatment and have 20mgKOH/g or lower acid number biodiesel raw material oil to remove external material from biodiesel raw material oil; The biodiesel raw material oil of purifying is dewatered; The biodiesel raw material of dehydration oil is made to remove metallic cation by the solid acid catalyst reaction protection bed (protection bed: PBR) being provided with Zeo-karb, mixed with the biodiesel raw material oil passed through by methyl alcohol, the solid acid catalyst then making mixture pass through to be provided with solid acid catalyst reacts main bed (main bed) (main bed: PFR), there is esterification, the acid number of biodiesel raw material oil is adjusted to 5mgKOH/g or lower; And under basic catalyst exists, the biodiesel raw material oil with 5mgKOH/g or lower final acid number is reacted.
A second aspect of the present invention provides the method preparing biofuel, said method comprising the steps of: contain lower fatty acid by sorbent treatment and have oily more than the biodiesel raw material of 20mgKOH/g acid number to remove foreign matter from biodiesel raw material oil; The acid number of biodiesel raw material oil is adjusted to 20mgKOH/g or lower by the continuous stirred tank reactor (CSTR) (CSTR) that is provided with enzyme catalyst there is esterification and transesterification reaction under existing at methyl alcohol, water and buffered soln and the content of FAME is adjusted to 60% or lower, then separation of glycerin by the biodiesel raw material of purifying oil; Biodiesel raw material oil is dewatered; Make the biodiesel raw material of dehydration oil by being provided with the solid acid catalyst reaction protection bed of Zeo-karb to remove positively charged ion, by methyl alcohol with reacted by solid acid catalyst protect the biodiesel raw material of bed oil mix, the solid acid catalyst then making mixture pass through to be provided with solid acid catalyst reacts main bed, there is esterification, the final acid number of biodiesel raw material oil is adjusted to 5mgKOH/g or lower; And under basic catalyst exists, the biodiesel raw material oil with 5mgKOH/g or lower final acid number is reacted.
First or second aspect, the biodiesel raw material oil with lower fatty acid can be selected from least one of lower group: rudimentary cooking waste oil, palmitic acid oil, brown grease, white grease, yellow grease, dark oil, oil removal and unpurified animal oil & fat.
First or second aspect, can implement to remove by the sorbent material adding 0.1-5 % by weight under the reaction times of the temperature of reaction of 30-150 DEG C and 15 minutes-3 hours the step of foreign matter.
First or second aspect, sorbent material can be selected from least one of lower group: diatomite, acidic white clay, active white clay, gac and Magnesium Silicate q-agent.
In second aspect, the buffered soln not producing saponification can be selected from least one of lower group: sodium hydrogen carbonate solution, sodium carbonate solution, sodium radio-phosphate,P-32 solution, 3-(N-morpholine) propanesulfonic acid solutions, (2-(N-morpholine) ethyl sulfonic acid solution, piperazine-N, N '-two (2-ethanesulfonic acid) solution and (N-(2-hydroxyethyl) piperazine (2-ethanesulfonic acid) solution, and add buffered soln until the pH of biodiesel raw material oil is in the scope of 6-7.9.
First or second aspect, in the step that biodiesel raw material oil is dewatered, water can be removed until the content of water is 0.1 % by weight or lower.
In second aspect, before the step that biodiesel raw material oil is dewatered, for enzyme catalyst reaction biodiesel raw material oil can with not containing foreign matter and have 20mgKOH/g or lower acid number biodiesel raw material oil with 1: 1 weight ratio mix, to regulate the content to 40% of FAME or lower.
In second aspect, can under the temperature of reaction of 20-40 DEG C, adopt the water (the biodiesel raw material oil based on 100 weight parts) of the alcohol of the catalyzer of 20-60 weight part, 1-20 weight part, 1-10 weight part, with by the pH regulator of biodiesel raw material oil to the buffered soln of 6-7.9, enzyme catalyst reaction can be implemented.
First or second aspect, temperature condition can be 20-80 DEG C, and the through-rate in solid acid catalyst reaction protection bed can be 6 volume % (6 SV) or lower.
First or second aspect, temperature condition can be 70-120 DEG C, and can be 0.5-1.5 SV in the through-rate that solid acid catalyst reacts in main bed.
First or second aspect, basic catalyst can be selected from least one in lower group: sodium methylate (NaOCH 3), sodium hydroxide (NaOH), potassium methylate (KOCH 3) and potassium hydroxide (KOH).
First or second aspect, under the reaction times of the temperature of reaction of 50-80 DEG C and 10 minutes-2 hours, the reactions steps of biodiesel raw material oil can be implemented under basic catalyst exists.
Beneficial effect
Beneficial effect of the present invention is as follows.
1. by removing impurity to the pre-treatment of biodiesel raw material oil from the biodiesel raw material oil containing a large amount of non-purifying impurity, solve following problem thus: the operation of blocking biofuel Preparation equipment, yield of biodiesel reduces and after biodiesel synthesis, is difficult to separating bio diesel oil and glycerine.
2., because of the use according to enzyme catalyst and solid acid catalyst, the restriction on the content of raw material type and FFA (free fatty acids) disappears, so the selectivity of biodiesel raw material becomes wide in range.
3., because the methyl alcohol used in enzyme catalyst reaction is not especially by the impact of water-content, reclaim methyl alcohol after can using in the reaction and do not need to carry out dewatering process, therefore do not need extra equipment and can cut down finished cost.
4. when raw material contains a large amount of lipid acid, because need acidification step, so common base catalysis agent method becomes complicated.But, because the present invention is by the impact of fatty acid content, can Simplified flowsheet, and by FFA being converted into biofuel instead of removing the output that FFA can improve biofuel from raw material.
5. owing to containing high metal-salt as the glycerine of the by product obtained in usual base catalysis agent method, its quality is lower, and therefore needs complicated refinery practice to obtain highly purified glycerine.But, due to the glycerine not metal-containing salt obtained in the present invention, so can refinement step be simplified.
Accompanying drawing explanation
By reference to the accompanying drawings, above and other object of the present invention, characteristic and other advantages more clearly can be understood by following detailed description, wherein:
Fig. 1 is the schematic diagram that display comprises the solid acid catalyst reactor according to protection bed of the present invention and main bed; And
Fig. 2 is the method for biofuel is prepared in display schema according to the present invention.
Reference numeral
10: stock oil
20: protection bed
30: mixing kettle
40: pump
50: main bed
60: pressure controlled valve
70: condenser
Preferred forms
Before describing the present invention in detail, the term used in the present invention and claim and vocabulary should not be construed as and is limited to common implication or dictionary definition, but should be interpreted as describing the rule of carrying out the best approach of the present invention known to him or she based on the concept that suitably can define term according to contriver, there is the implication relevant to technical scope of the present invention and concept.
Describe the preferred embodiment of the present invention in detail below with reference to accompanying drawing, make those skilled in the art easily can realize the present invention.In addition, in describing the invention, when determining that the detailed description of association area can make main idea of the present invention smudgy, its description can be omitted.
Usually, by reacting with the oil & fat of animal and plant and fatty alcohol under basic catalyst existence, with reactant of esterification, biofuel is prepared.In various biodiesel oil preparing process, the most frequently used method being prepared biofuel by basic catalyst.At present, sodium methylate (NaOCH is usually used 3) as basic catalyst, and also use sodium hydroxide (NaOH), potassium methylate (KOCH 3), potassium hydroxide (KOH) etc.Even if usually use the reason of sodium methylate to be costly still high yield to obtain biofuel when raw material contains water why.
Except above-mentioned general biodiesel oil preparing process, also there is several biodiesel oil preparing process.Such as, exist, the first, under existing at acid catalyst (as sulfuric acid), at high temperature and pressure, make the oil & fat of animal and plant and fatty alcohol react the method preparing biofuel; The second, by the oil & fat of animal and plant is hydrogenated to lipid acid, then in presence of an acid catalyst this lipid acid and fatty alcohol are reacted the method preparing biofuel; 3rd, by using insoluble catalyzer (as barium oxide), the oil & fat of animal and plant and fatty alcohol are reacted the method preparing biofuel; With, the 4th, by using enzyme catalyst (as lipase), animal and plant oil & fat and fatty alcohol are reacted the method etc. preparing biofuel.
The invention provides from there is 5mgKOH/g or more high acid value and maximum acid number are economical the biodiesel raw material oil of 200mgKOH/g and prepare the method for biofuel efficiently containing lower fatty acid.
First, according to one aspect of the present invention, provide the combination using solid acid catalyst and base metal catalysts, from there is 5mgKOH/g or more high acid value and maximum acid number are economical the biodiesel raw material oil of 200mgKOH/g and prepare the method for biofuel efficiently containing lower fatty acid.
In addition, according to another aspect of the present invention, provide and use the combination of enzyme catalyst, solid acid catalyst and base metal catalysts, from having economical the biodiesel raw material oil more than the acid number of 20mgKOH/g containing lower fatty acid and prepare the method for biofuel efficiently.
1. the pre-treatment of stock oil
According to the present invention, to there is the acid number of 5mgKOH/g or more and maximum acid number is add sorbent material in the biodiesel raw material oil of 200mgKOH/g containing lower fatty acid, to remove a large amount of outer material materials from biodiesel raw material oil, such as particulate matter, glue, soap and moisture etc.
In the present invention, the biodiesel raw material oil (hereinafter referred to as " stock oil ") with lower fatty acid can be selected from least one of lower group: rudimentary cooking waste oil, palmitic acid oil, brown grease, white grease, yellow grease, dark oil, oil removal and unpurified animal oil & fat.But stock oil is not limited to this, as long as and they as the raw material of biofuel, just can use all stock oil.
Lower fatty acid, such as brown grease etc., produce the foreign matter of all size in source containing with good grounds its and produce stink.Therefore, multiple various flocculating aids can be used, but in the present invention, preferably use sorbent material, because it has outstanding adsorptivity, deodorizing capability and humid control performance to show the effect absorbing foreign matter in lower fatty acid, remove stink and reduce humidity.The example showing the sorbent material of this kind of effect comprises diatomite, white clay (acidic white clay, active white clay etc.), gac and/or magnesium (Magnesium Silicate q-agent).Preferred diatomite is as sorbent material.The amount of sorbent material can be 0.1-5 % by weight.When its amount lower than 0.1 % by weight time, its addition effect is not enough, and when its amount is more than 5 % by weight, sorbent material tends to absorption stock oil, and this is not preferred.
At 30-150 DEG C, at the temperature of preferred 50-80 DEG C, implement absorption reaction.According to its source, rudimentary stock oil (as brown grease, rudimentary cooking waste oil, palmitic acid oil, yellow grease, dark wet goods) may comprise a large amount of saturated fatty acids.In the pretreatment technology using this stock oil, at room temperature the mobility of stock oil declines.Therefore, in order to ensure its mobility, stock oil is heated (Heating temperature according to the content feed change oil of saturated fatty acid in stock oil), make stock oil and sorbent material fully thus and effectively react.
The absorption reaction in pretreatment technology can be implemented under the reaction times of the temperature of reaction of 30-150 DEG C and 15 minutes-3 hours.When under the temperature of reaction of 50-80 DEG C, implement absorption reaction and the reaction times be 30 minutes-1.5 constantly little, the ability of adsorbent foreign matter is best.When absorption reaction completes, by pressure filter, leaf filter or centrifuge separator, the stock oil mixed with sorbent material is filtered.After filtration, the stock oil of filtration is preferably containing 1 % by weight or less 1 μm or less particle.Hereinafter, the stock oil of this filtration is called " pretreated stock oil " or " stock oil that pre-treatment is complete ".
2. react according to the stock oil of acid number
1) solid acid catalyst reaction
With reference to Fig. 1, as above-mentioned pre-treatment has the stock oil 10 of 20mgKOH/g or lower acid number, then dewater to remove water to pretreated stock oil until the content of water is 0.1 % by weight or lower.Subsequently; the stock oil of dehydration removes positively charged ion by the solid acid catalyst reaction protection bed 20 (PBR: packaging reactor beds) being provided with Zeo-karb; with methanol mixed in mixing kettle 30, then by pump 40 be provided to the solid acid catalyst being provided with solid acid catalyst react main bed 50 (PFR: plug flow reactor) with occur esterification implement solid acid catalyst reaction.Carry out this reaction product of condensation by condenser 70, be then transferred to follow-up technique.
Meanwhile, when the acid number of stock oil is 5mgKOH/g or lower, during preferred 2mgKOH/g or lower, reaction completes.When the acid number of stock oil is more than 5mgKOH/g, reclaim methyl alcohol, and stock oil reacts main bed further by solid acid catalyst is adjusted to 5mgKOH/g or lower by the final acid number of biodiesel raw material oil, preferred 2mgKOH/g or lower, its be adapted so that after the maximizing efficiency of basic catalyst technique.
In the present invention, the reason removing the water in stock oil is the generation of the solid acid catalyst reaction along with the solid acid catalyst using esterification, create water, and the water produced causes reversed reaction, and therefore the acid number of stock oil exceedes target acid number 5mgKOH/g.In addition, the reason removing metallic cation from stock oil is metallic cation and hydrogen ion (H +) cause substitution reaction together, reduce the activity of solid acid catalyst, because this reducing the life time of solid acid catalyst.In addition, the reason with the stock oil of 20mgKOH/g or lower acid number is used to be to be difficult to reach stock oil (product) the target acid number of 5mgKOH/g.
2) enzyme catalyst reaction and solid acid catalyst reaction
Pre-treatment has the stock oil of the acid number more than 20mgKOH/g, then be provided in the first and second continuous stirred tank reactor (CSTR)s (CSTR) successively, it is provided with the enzyme catalyst for esterification and transesterification reaction separately, implements enzyme catalyst reaction until the acid number of enzyme catalyst reaction product (stock oil) is 20mgKOH/g or lower.In this enzyme catalyst reaction, create glycerine, and be separated this glycerine by gravity separation or centrifugation.
The stock oil of enzyme catalyst reaction with not containing foreign matter and the stock oil with 20mgKOH/g or lower acid number with 1: 1 or 1: 2 or higher weight ratio (such as, 1: 2,1: 3 etc.) mix.Then; dewater to remove water and methyl alcohol to the stock oil of mixing; and be supplied to solid acid catalyst reaction protection bed (PBR) being provided with Zeo-karb subsequently successively and remove positively charged ion; and the solid acid catalyst being provided with solid acid catalyst reacts main bed (PBR) there is esterification, implement solid acid catalyst reaction.
In this case, the stock oil of the weight ratio mixed enzyme catalyst reaction with 1: 1 or 1: 2 or higher with not containing foreign matter and the reason with the stock oil of 20mgKOH/g or lower acid number be, when there being the content of lipid acid methyl ether (FAME) in stock oil, due to the water produced in solid acid catalyst reaction, the solid acid catalyst of esterification causes reversed reaction, and therefore the acid number of stock oil (product) exceedes target acid number 5mgKOH/g.
Preparing in the method for biofuel according to the present invention, pretreated stock oil mixes with methyl alcohol, water and buffered soln, then mixture reaction in the continuous stirred tank reactor (CSTR) (CSTR) of enzyme catalyst being provided with esterification and transesterification reaction.
Meanwhile, buffered soln, it, for not participating in reaction by neutralization reactant simultaneously, makes the pH of reactant change to the solution of neutral position, must not cause saponification.According to the present invention, all buffered soln with 9 or higher pKa can use without restriction, as long as they do not produce the by product of such as soap etc. while regulating pH.
The example of the buffered soln of saponification is not caused to comprise: sodium hydrogen carbonate solution; Sodium carbonate solution; Sodium radio-phosphate,P-32 solution is (as Na 2hPO 42H 2o or NaH 2pO 42H 2o); 3-(N-morpholine) propanesulfonic acid solutions; With ethyl sulfonic acid solution (as (2-(N-morpholine) ethyl sulfonic acid solution, piperazine-N, N '-two (2-ethanesulfonic acid) solution or (N-(2-hydroxyethyl) piperazine (2-ethanesulfonic acid) solution).
Add buffered soln until the pH scope of stock oil is 6-7.9, and the stock oil with above-mentioned pH scope can maximize the activity of enzyme catalyst in the process of preparation biofuel.As above-mentioned, buffered soln can regulate the pH of stock oil, and must not cause saponification.When adding general pH adjusting agent in stock oil, causing saponification, therefore need the subsequent technique removing soap, and the output of biofuel significantly reducing.
3) enzyme catalyst and enzyme catalyst reaction conditions
As the enzyme catalyst used in the present invention, can commercial use 40 kinds or more the lipase of planting and Phospholipid hydrolase, but the round plastic vehicle with 2-3mm diameter preferably supported by this enzyme catalyst.
Meanwhile, be applicable to biodiesel raw material of the present invention oil, the stock oil of such as purifying, such as soybean oil, rapeseed oil, palm wet goods can use without pre-treatment.But, in the present invention, can use be selected from lower group one or both or more plant mixture to prepare biofuel: palmitic acid oil, cooking waste oil, brown grease, dark oil, white grease, yellow grease, oil removal and unpurified animal and plant oil & fat.In addition, the stock oil containing lipid acid can be used to prepare biofuel, described lipid acid is produced by the crude glycerol produced in preparation of biodiesel.Usually, biodiesel raw material oil can be used without restriction, as long as its pH is 6-8 and containing the particle with 1 % by weight or lower 1 μm or more minor diameter.
Subsequently stock oil is supplied to successively and is provided with in first and second continuous stirred tank reactor (CSTR)s (CSTR) of enzyme catalyst, for the measurement acid number according to stock oil, the esterification under alcohol, water and/or buffered soln exist and transesterification reaction.
Enzyme catalyst for esterification and transesterification reaction is the catalyzer by the esterification of FFA or the transesterification reaction synthesizing fatty acid methyl ester (FAME) of monoglyceride, triglyceride or triglyceride level.
Usually, at 20-40 DEG C, implement enzyme catalyst reaction.Enzyme catalyst uses with the amount of 20-60 weight part, and alcohol uses with the amount of 1-20 weight part and water uses with the amount of 1-10 weight part, based on the biodiesel raw material oil of 100 weight parts.Adding buffered soln makes the pH of stock oil be 6-7.9.
4) solid acid catalyst reaction conditions
Before solid acid catalyst esterification, the water-content in stock oil (charging) can be controlled 0.1 % by weight or lower.The dewatered product of pretreated dehydration stock oil and enzyme product can the mode of following current through solid acid catalyst reaction protection bed (Zeo-karb) to remove metallic cation.In this case, at 20-80 DEG C, implement this process, and they pass through protection bed with 6 volume % (6 SV) or lower flow rate.These conditions have superiority in economic interests and reaction efficiency.
React in main bed at solid acid catalyst, the stock oil of pre-treatment (removing foreign matter, dehydration and removal positively charged ion) and methyl alcohol (10-50 % by weight, based on stock oil) or the methanol mixed of enzyme catalyst reaction product, then mixture carries out solid catalyst reaction (temperature of reaction: 70-120 DEG C in a counter-current fashion through first and second packed bed reactors (PBR) of the solid acid catalyst being provided with esterification successively, reaction flow velocity: 0.5-1.5 SV, reactor input and output (in-out) p:2.0kgf/cm 2or lower).
3. basic catalyst reaction
In biodiesel oil preparing process, usually use base catalysis agent method.In this article, sodium methylate (NaOCH 3), sodium hydroxide (NaOH), potassium methylate (KOCH 3) and/or potassium hydroxide (KOH) can basic catalyst be used as.In the present invention, when the acid number of product in process be before 2-5mgKOH/g and its water-content lower than 0.5 % by weight time, use potassium hydroxide catalyst; When its acid number be 2mgKOH/g or lower and its water-content lower than 0.5 % by weight time, use sodium hydroxide catalyst; When its acid number is 2-5mgKOH/g and its water-content is 0.5-1 % by weight, use potassium methylate catalyzer; And when its acid number is 2mgKOH/g or lower and its water-content is 0.5-1 % by weight, use sodium methoxide catalyst.In this case, when the acid number of stock oil is 5.0mgKOH/g or higher, after base metal catalysts reaction, the output of biofuel reduces fast, because this reducing economical efficiency, and its acid number does not meet the quality standard (5.0mgKOH/g or lower) of automobile fuel, and therefore preferably use the stock oil that acid number is 5.0mgKOH/g or lower.
The product obtained by use above-mentioned solid acid catalyst according to its acid number and water-content under the temperature of reaction of the 50-80 DEG C solid acid catalyst process of 10 minutes-2 hours is reacted and produces biofuel and glycerine.Separation of glycerin is carried out by gravity separation or centrifugation.Pass through, if needed, the new high-grade stock oil that can have 5mgKOH/g or lower acid number by mixing and the product obtained from solid acid catalyst processes implement base catalysis agent method.In this case, basic catalyst reaction can be implemented by adding not enough methyl alcohol.Meanwhile, above-mentioned conduction is preferred in economic interests and reaction efficiency.
Invention embodiment
Hereinafter, in more detail the present invention is described with reference to following examples and comparative example.But scope of the present invention is not limited to these embodiments.
Embodiment 1
In the 1000g brown grease (BG) of the water content of the acid number and 0.5% with about 19.9mgKOH/g, add the diatomite of 20g, then react 1 hour at about 70 DEG C.Its reaction conditions and result are shown in table 1 below.
Table 1
Comparative example 1
In the 1000g brown grease (BG) of the water content of the acid number and 0.5% with about 19.9mgKOH/g, add the diatomite of 70g, then react 1 hour at about 70 DEG C.Its reaction conditions and result are shown in table 2 below.
Table 2
As shown in Tables 1 and 2, can determine that in embodiment 1, the output of biofuel is 99.11% and does not change the acid number of brown grease, and it adds 4.49% compared with the output of biofuel in comparative example 1 when using the diatomite of appropriate amount.
Embodiment 2
To the 1000g stock oil of the acid number with about 19.8mgKOH/g, (FFA: about 10%, triglyceride level: the diatomite adding 20g about 90%), then reacts and obtains biodiesel raw material oil in about 1 hour at about 70 DEG C.The biodiesel raw material oil of gained comprises the particle with 1 μm or lower diameter of about 0.6 % by weight.
According to Fig. 2 application 1 shown in the reaction conditions that provides in the following Table 3 of reaction sequence under carry out the reaction of biodiesel raw material oil.Solid acid catalyst for removing cationic protection bed can be provided with K2629 tMthe Zeo-karb of (being produced by the LANXESS company of Germany).Solid acid catalyst for the main bed of esterification can be provided with GF-101 tMthe SO that (being produced by the LANXESS company of Germany) fluoropolymer resin is supported 3h +.
In this embodiment, by stock oil and the methanol mixed of solid acid catalyst protection bed, and mixture reacts in the main bed of solid acid catalyst, obtains the stock oil of the acid number with 1.94mgKOH/g thus.
Table 3
Embodiment 3
To the 1000g stock oil of the acid number with about 49.4mgKOH/g, (FFA: about 24.7%, triglyceride level: the diatomite adding 20g about 75.3%), then reacts and obtains biodiesel raw material oil in about 1 hour at about 70 DEG C.The biodiesel raw material oil of gained comprises the particle with 1 μm or lower diameter of about 0.5 % by weight.
According to Fig. 2 application 2 shown in the reaction conditions that provides in the following Table 4 of reaction sequence under carry out the reaction of biodiesel raw material oil.CSTR is provided with the enzyme catalyst (TRANSZYME produced by the TRASBIODIESEL company of Israel tM), wherein support lipase with plastics.Zeo-karb (the K2629 produced by the LANXESS company of Germany is provided with for removing cationic solid acid catalyst protection bed tM).The main bed of solid acid catalyst for the esterification is provided with (GF-101 produced by the LANXESS company of Germany tM) fluoropolymer resin support SO 3h +.
In this embodiment, from pretreated stock oil, remove glycerine (it is the by product of enzyme catalyst reaction in CSTR) and the water etc. of about 15 weight parts.This stock oil with have 20mgKOH/g or lower acid number pretreated stock oil with 1: 1 (% by weight) ratio mix, dehydration, be then supplied in solid acid catalyst protection bed.By stock oil and the methanol mixed of solid acid catalyst protection bed, and mixture reacts in the main bed of solid acid catalyst, obtains the stock oil of the acid number with 1.91mgKOH/g thus.
Table 4
Embodiment 4
To the 1000g stock oil of the acid number with about 99.5mgKOH/g, (FFA: about 49.75%, triglyceride level: the diatomite adding 20g about 50.25%), then reacts and obtains biodiesel raw material oil in about 1 hour at about 70 DEG C.The biodiesel raw material oil of gained comprises the particle with 1 μm or lower diameter of about 0.4 % by weight.
According to Fig. 2 application 2 shown in the reaction conditions that provides in the following Table 5 of reaction sequence under carry out the reaction of biodiesel raw material oil.CSTR is provided with the enzyme catalyst (TRANSZYME of the TRASBIODIESEL company production of Israel tM), wherein lipase supported by plastics, is provided with the Zeo-karb (K2629 of the LANXESS company production of Germany for removing cationic solid acid catalyst protection bed tM), and the main bed of solid acid catalyst of esterification is provided with the fluoropolymer resin (GF-101 of the LANXESS company production of Germany tM) SO that supports 3h +.
In this embodiment, from pretreated stock oil, remove glycerine (it is the by product of enzyme catalyst reaction in CSTR 1) and the water etc. of about 15 weight parts, then this stock oil is supplied to CSTR 2.Then, from pretreated stock oil, remove glycerine (it is the by product of enzyme catalyst reaction in CSTR 2) and the water etc. of about 15 weight parts.This stock oil with have 20mgKOH/g or lower acid number pretreated stock oil with 1: 1 (% by weight) ratio mix, dehydration, be then supplied in solid acid catalyst protection bed 1.By stock oil and the methanol mixed of solid acid catalyst protection bed 1, and mixture reacts in the main bed 1 of solid acid catalyst, obtains the stock oil of the acid number with 1.73mgKOH/g thus.
Table 5
Embodiment 5
To the 1000g stock oil of the acid number with about 148.6mgKOH/g, (FFA: about 74.3%, triglyceride level: the diatomite adding 20g about 25.7%), then reacts and obtains biodiesel raw material oil in about 1 hour at about 70 DEG C.The biodiesel raw material oil of gained comprises the particle with 1 μm or lower diameter of about 0.6 % by weight.
According to Fig. 2 application 2 shown in the reaction conditions that provides in the following Table 6 of reaction sequence under carry out the reaction of biodiesel raw material oil.CSTR is provided with the enzyme catalyst (TRANSZYME of the TRASBIODIESEL company production of Israel tM), wherein lipase supported by plastics, is provided with the Zeo-karb (K2629 of the LANXESS company production of Germany for removing cationic solid acid catalyst protection bed tM), and the main bed of solid acid catalyst of esterification is provided with the fluoropolymer resin (GF-101 of the LANXESS company production of Germany tM) SO that supports 3h +.
In this embodiment, from pretreated stock oil, remove glycerine (it is the by product of enzyme catalyst reaction in CSTR 1) and the water etc. of about 15 weight parts, then this stock oil is supplied to CSTR 2.Then, from pretreated stock oil, remove glycerine (it is the by product of enzyme catalyst reaction in CSTR 2) and the water etc. of about 15 weight parts.This stock oil with have 20mgKOH/g or lower acid number pretreated stock oil with 1: 1 (% by weight) ratio mix, dehydration, be then supplied in solid acid catalyst protection bed 1.By stock oil and the methanol mixed of solid acid catalyst protection bed 1, and this mixture reacts in the main bed 1 of solid acid catalyst.Dewater therefrom to remove water and methyl alcohol to the reaction product in the main bed 1 of solid acid catalyst, then react with methanol mixed in the main bed 2 of solid acid catalyst further, obtain the stock oil of the acid number with 2.04mgKOH/g thus.
Table 6
Embodiment 6
Obtain in example 4 there is the acid number of about 1.73mgKOH/g stock oil (FFA: about 1.0%, triglyceride level: about 60%, FAME: react under the reaction conditions that about 39%) table 7 provides below.The sodium methoxide catalyst used in basic catalyst reaction is NM25 tM(being produced by the EVONIK company of Germany).The stock oil of 100 weight parts and the sodium methylate (NaOCH of 2.0 weight parts 3) Homogeneous phase mixing, then react at the temperature of about 70 DEG C and obtain biofuel and glycerine in about 0.5 hour.The output of biofuel relative raw material oil is about 98 weight parts, and the output of glycerine relative raw material oil is about 6 weight parts.The biofuel of gained have 0.16mgKOH/g acid number and containing 97.8% or more FAME.
Table 7
Embodiment 7
Obtain in embodiment 5 there is the acid number of about 2.04mgKOH/g stock oil (FFA: about 1.0%, triglyceride level: about 60%, FAME: react under the reaction conditions that about 39%) table 8 provides below.The potassium methylate catalyzer used in basic catalyst reaction is KM32 tM(being produced by the EVONIK company of Germany).The stock oil of 100 weight parts and the potassium methylate (KOCH of 1.5 weight parts 3) Homogeneous phase mixing, then react at the temperature of about 70 DEG C and obtain biofuel and glycerine in about 30 minutes.The output of biofuel relative raw material oil is about 98 weight parts, and the output of glycerine relative raw material oil is about 6 weight parts.The biofuel of gained have 0.17mgKOH/g acid number and containing 97.4% or more FAME.
Table 8

Claims (13)

1. prepare a method for biofuel, said method comprising the steps of:
With sorbent material from having the biodiesel raw material oil of 20mgKOH/g or lower acid number remove foreign matter containing lower fatty acid;
The described biodiesel raw material oil eliminating foreign matter is dewatered;
At 20-80 DEG C, make the described biodiesel raw material through dehydration oil by being provided with the solid acid catalyst reaction protection bed of Zeo-karb to remove metallic cation with 6 volume % (6 SV) or lower flow velocity, methyl alcohol is mixed with the described biodiesel raw material oil passed through, then at 70-120 DEG C, with the flow velocity of 0.5-1.5 SV, described mixture is reacted main bed there is esterification by the solid acid catalyst being provided with solid acid catalyst, the final acid number of described biodiesel raw material oil is adjusted to 5mgKOH/g or lower; And
The biodiesel raw material oil described in making under basic catalyst exists with the final acid number of 5mgKOH/g or lower reacts.
2. prepare a method for biofuel, said method comprising the steps of:
With sorbent material from having the biodiesel raw material oil more than the acid number of 20mgKOH/g remove foreign matter containing lower fatty acid;
The biodiesel raw material oil eliminating foreign matter described in making carries out esterification and transesterification reaction by the continuous stirred tank reactor (CSTR) (CSTR) being provided with enzyme catalyst under existing at methyl alcohol, water and buffered soln, the acid number of described biodiesel raw material oil is adjusted to 20mgKOH/g or lower and the content of FAME is adjusted to 60% or lower, then separation of glycerin;
Described biodiesel raw material oil is dewatered;
By the described oil of the biodiesel raw material through dehydration by being provided with the solid acid catalyst reaction protection bed of Zeo-karb to remove metallic cation, mixing methyl alcohol and the described biodiesel raw material oil by described solid acid catalyst reaction protection bed, then make described mixture react main bed there is esterification by the solid acid catalyst being provided with solid acid catalyst, the final acid number of described biodiesel raw material oil is adjusted to 5mgKOH/g or lower; And
The biodiesel raw material oil described in making under basic catalyst exists with the final acid number of 5mgKOH/g or lower reacts.
3. method as claimed in claim 1 or 2, it is characterized in that, the described at least one of biodiesel raw material grease separation in lower group containing lower fatty acid: rudimentary cooking waste oil, palmitic acid oil, brown grease, white grease, yellow grease, dark oil, oil removal and unpurified animal oil & fat.
4. method as claimed in claim 1 or 2, is characterized in that, is implemented the step of described removal foreign matter by the sorbent material adding 0.1-5 % by weight under the reaction times of the temperature of reaction of 30-150 DEG C and 15 minutes-3 hours.
5. method as claimed in claim 1 or 2, it is characterized in that, described sorbent material is selected from least one in lower group: diatomite, acidic white clay, active white clay, gac and Magnesium Silicate q-agent.
6. method as claimed in claim 2, it is characterized in that, described buffered soln can be selected from least one in lower group: sodium hydrogen carbonate solution, sodium carbonate solution, sodium radio-phosphate,P-32 solution, 3-(N-morpholine) propanesulfonic acid solutions, (2-(N-morpholine) ethyl sulfonic acid solution, piperazine-N, N '-two (2-ethanesulfonic acid) solution and (N-(2-hydroxyethyl) piperazine (2-ethanesulfonic acid) solution, and add described buffered soln until the pH of described biodiesel raw material oil is in the scope of 6-7.9.
7. method as claimed in claim 1 or 2, implements described step of dewatering to described biodiesel raw material oil until water content is 0.1 % by weight or lower.
8. method as claimed in claim 2, it is characterized in that, before the step that described biodiesel raw material oil is dewatered, the biodiesel raw material oil reacted from described enzyme catalyst with eliminate foreign matter and the oily weight ratio with 1: 1 or higher of biodiesel raw material with 20mgKOH/g or lower acid number mixes, so that the content of FAME is adjusted to 40% or lower.
9. method as claimed in claim 2, it is characterized in that, under the temperature of reaction of 20-40 DEG C, be 100 parts by weight with described biodiesel raw material oil, adopt the catalyzer of 20-60 weight part, the alcohol of 1-20 weight part, the water of 1-10 weight part and the pH regulator of described biodiesel raw material oil to the buffered soln of 6-7.9 can be implemented the reaction of described enzyme catalyst.
10. method as claimed in claim 2, is characterized in that, the described oil of the biodiesel raw material through dehydration reacts protection bed with 6 volume % (6 SV) or lower flow velocity by described solid acid catalyst at 20-80 DEG C.
11. methods as claimed in claim 2, is characterized in that, described biodiesel raw material oil reacts main bed with the flow velocity of 0.5-1.5 SV by described solid acid catalyst with the mixture of methyl alcohol at the temperature of 70-120 DEG C.
12. methods as claimed in claim 1 or 2, it is characterized in that, described basic catalyst is selected from least one in lower group: sodium methylate (NaOCH 3), sodium hydroxide (NaOH), potassium methylate (KOCH 3) and potassium hydroxide (KOH).
13. methods as claimed in claim 1 or 2, is characterized in that, under the reaction times of the temperature of reaction of 50-80 DEG C and 10 minutes-2 hours, implement the reactions steps of described biodiesel raw material oil under basic catalyst exists.
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